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811.
Patteux C Foucout L Bohn P Dupas G Leprince J Tonon MC Dehouck B Marsais F Papamicaël C Levacher V 《Organic & biomolecular chemistry》2006,4(5):817-825
A solid phase approach for the preparation of peptides attached to a redox chemical delivery system derived from stable annulated NADH models is reported. The synthesis starts with the grafting on a Merrifield resin of quinoline 4b, precursor of the redox carrier. From the resulting quinoline supported resin 4d, the stepwise SPPS of both octapeptide OP (RPGLLDLK) and octadecaneuropeptide ODN (QATVGDVNTDRPGLLDLK), two neuropeptides exhibiting anorexigenic effects, was successfully achieved by conventional methods. Quaternization of the quinoline moiety prior to cleavage of the modified OP and ODN peptides from the resin, led to the expected quinolinium salt 8a and 8b respectively linked to OP or ODN peptides. Finally, the reduction with NaBH4 monitored by UV-vis, provided the desired annulated NADH models as peptides carriers with either the OP (11a,b) or ODN (12a,b) moiety. 相似文献
812.
8-vinyl-adenosine (8VA) is a new fluorescent nucleoside analogue with improved spectroscopic properties as compared to 2-aminopurine (2AP). To further understand its photophysics, we analyzed by the time-dependent density functional theory and the configuration interaction single method, the electronic properties, and transitions of 8VA in its free form and stacked with one or two flanking bases. For free 8VA, the predicted excited-state energy gaps, absorbance peak position, and oscillator strength were found to be in excellent agreement with the experimentally determined ones. Moreover, its high fluorescence quantum yield was found to be associated with the dipole-allowed S1 --> S0 transition. Stacking of 8VA with C, T, or A in dimers or trimers resulted in fluorescence quenching through mechanisms that depend on the nature and relative orientation of the flanking base(s). When 8VA is stacked with T, quenching mainly results from nonradiative relaxation to low-lying dark excited state(s) that do not exist in free 8VA. When 8VA is stacked with A, quenching results mainly from mixing of the molecular orbitals in the ground state. Both types of quenching are thought to accompany the stacking of 8VA with C. In addition, the C-8VA-C trimer was found to exhibit a low-lying S1 emissive state that may generate an increased fluorescence quantum yield and lifetime. The predicted photophysical properties of the trimers are highly consistent with the spectroscopic data of a series of 15-mer oligonucleotides differing only by the nature of the residues flanking the central 8VA. 相似文献
813.
Highly stable triazatriangulenium carbocations, of pK(R+) higher than 20, can be used as novel phase-transfer catalysts for several classical organic reactions, their intrinsic stability in strongly basic and nucleophilic conditions rendering this novel use feasible. 相似文献
814.
Analysis of type I and IV collagens by FT-IR spectroscopy and imaging for a molecular investigation of skeletal muscle connective tissue 总被引:2,自引:0,他引:2
Petibois C Gouspillou G Wehbe K Delage JP Déléris G 《Analytical and bioanalytical chemistry》2006,386(7-8):1961-1966
Many muscular diseases result from abnormal organization of connective tissue and/or collagen network formation. Only a few
molecular imaging techniques are able to analyze this collagen network by differentiating collagen types. In this study, FT-IR
spectroscopy was used to analyze type I and IV collagens, the most important compounds of which are perimysium and endomysium,
respectively. Secondary structure of collagen types was determined by curve-fitting the 1,700–1,480 cm−1 spectral interval. Type I collagen could be differentiated from type IV by its higher amounts of triple helix and α-helix,
but lower amounts of β-sheets (P < 0.01). FT-IR imaging was then used to determine structural features of perimysium and endomysium collagen network in bovine
Flexor carpi radialis muscle. Secondary structure of proteins contained in perimysium and endomysium was found to be very close to type I and IV
collagens, respectively. FT-IR spectroscopy and imaging are thus analytical tools that might be used for investigating biodistribution
and assembly of collagen types in connective tissues.
Figure Visible (left) and full spectral FT-IR (right) images of skeletal muscle tissue section (16 μm) exhibiting a vertical arrangement of fibers. + and × in FT-IR image show
selected positions to obtain FT-IR spectra of perimysium and endomysium, respectively 相似文献
815.
Cugnet C Lucas D Lemaître F Collange E Soldera A Mugnier Y Harvey PD 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(32):8386-8395
The title cluster, [Pd(3)(mu(3)-CO)(dppm)(3)](2+) (dppm=bis(diphenylphosphino)methane), reacts with one equivalent of hydroxide anions (OH(-)), from tetrabutylammonium hydroxide (Bu(4)NOH), to give the paramagnetic [Pd(3)(mu(3)-CO)(dppm)(3)](+) species. Reaction with another equivalent of OH(-) leads to the zero-valent compound [Pd(3)(mu(3)-CO)(dppm)(3)](0). From electron paramagnetic resonance analysis of the reaction medium using the spin-trap agent 5,5-dimethyl-1-pyrroline-N-oxide (DMPO), the 2-tetrahydrofuryl or methyl radicals, deriving from the tetrahydrofuran (THF) or dimethyl sulfoxide (DMSO) solvent, respectively, were detected. For both [Pd(3)(mu(3)-CO)(dppm)(3)](2+) and [Pd(3)(mu(3)-CO)(dppm)(3)](+), the mechanism involves, in a first equilibrated step, the formation of a hydroxide adduct, [Pd(3)(mu(3)-CO)(dppm)(3)(OH)]((n-1)+) (n=1, 2), which reacts irreversibly with the solvent. The kinetics were resolved by means of stopped-flow experiments and are consistent with the proposed mechanism. In the presence of an excess of Bu(4)NOH, an electrocatalytic process was observed with modest turnover numbers (7-8). The hydroxide adducts [Pd(3)(mu(3)-CO)(dppm)(3)(OH)]((n-1)+) (n=1, 2), which bear important similarities to the well-known corresponding halide adducts [Pd(3)(mu(3)-CO)(dppm)(3)(mu(3)-X)](n) (X=Cl, Br, I), have been studied by using density functional theory (DFT). Although the optimised geometry for the cluster in its +2 and 0 oxidation states (i.e., cation and anion clusters, respectively) is the anticipated mu(3)-OH form, the paramagnetic species, [Pd(3)(mu(3)-CO)(dppm)(3)(OH)](0), shows a mu(2)-OH form; this suggests an important difference in electronic structure between these three species. 相似文献
816.
Colas C Garcia P Popot MA Bonnaire Y Bouchonnet S 《Rapid communications in mass spectrometry : RCM》2006,20(22):3257-3266
A method has been developed for the analysis and characterization in equine urine and plasma of iridoid glycosides: harpagide, harpagoside and 8-para-coumaroyl harpagide, which are the main active principles of Harpagophytum, a plant with antiinflammatory properties. The method involves liquid chromatography coupled with positive electrospray ionization mass spectrometry. The addition of sodium or lithium chloride instead of formic acid in the eluting solvent has been studied in order to enhance the signal and to modify the ion's internal energy. Fragmentation pathways and associated patterns are proposed for each analyte. A comparison of three types of mass spectrometer: a 3D ion trap, a triple quadrupole and a linear ion trap, has been conducted. The 3D ion trap was selected for drug screening analysis whereas the linear ion trap was retained for identification and quantitation analysis. 相似文献
817.
Barsu C Fortrie R Nowika K Baldeck PL Vial JC Barsella A Fort A Hissler M Bretonnière Y Maury O Andraud C 《Chemical communications (Cambridge, England)》2006,(45):4744-4746
The design of new chromophores presenting simultaneous SHG and TPEF properties is reported. 相似文献
818.
Growth hormone-releasing factor was discovered in 1982 by Guillemin and has been subjected to intense investigations because of its huge potential applications. The major concerns encountered with the native molecules were their short half-lives in vivo in many species including man, precluding the practical use of these peptides for medical or production purposes. Many efforts to produce analogs of shorter length, more resistant to degradation and having higher affinity to the receptors have been made during the last decades. The present paper presents a quick review of the work done to produce such analogs. 相似文献
819.
The starting point of this work is a paper by Alvarez, Lasry and Lions (1997) concerning the convexity and the partial convexity of solutions of fully nonlinear degenerate elliptic equations. We extend their results in two directions. First, we deal with possibly sublinear (but epi-pointed) solutions instead of 1-coercive ones; secondly, the partial convexity of C2 solutions is extended to the class of continuous viscosity solutions. A third contribution of this paper concerns C1,1 estimates for convex viscosity solutions of strictly elliptic nonlinear equations. To finish with, all the tools and techniques introduced here permit us to give a new proof of the Alexandroff estimate obtained by Trudinger (1988) and Caffarelli (1989). 相似文献
820.
In the search of new huprine-like acetylcholinesterase binders, we have developed an improved, shorter, and high-scalable synthetic pathway for the huprine synthesis based on a Reformatsky reaction-one-pot fragmentation/Friedländer condensation sequence. An extension for the one-pot synthesis of huprine-like 4-chloroquinolines is also presented. This modified route is particularly interesting as it allows to yield a huprine containing a functional group at position 9 in only three steps from commercially available material. 相似文献